本研究將針對NH4+去除，首度開發以鹼基為基礎的吸附材料，製備氨基修飾二氧化矽(NH2-SiO2)，研究中以四乙氧基矽烷(tetraethyl orthosilicate，TEOS)與(3-氨基丙基)三乙氧基矽烷((3-Aminopropyl)triethoxysilane，APTES)作為SiO2與-NH2來源，從FTIR圖譜中可以看到單純SiO2樣品中波數為798 cm-1的訊號代表Si-O-Si之鍵結，而不同APTES：TEOS比例之NH2-SiO2中，除SiO2的特徵峰外，在694cm-1多出N-H鍵結的訊號，表示-NH2成功地修飾在SiO2顆粒上。隨著APTES：TEOS比例從0：5增加至20：5，NH4+吸附量從無法量測增加至9.85 mg/g，表示-NH2為一有效吸附活性位址。再以動力吸附模式、等溫吸附模式、FTIR圖譜瞭解NH4+吸附行為與機制，結果顯示動力吸附模式較符合擬二階動力模式，其相關係數R2高達0.997，等溫吸附模式較符合Langmuir model，其相關係數為0.984且最大吸附量為11.53 mg/g，表示其速率決定步驟為NH4+與NH2-SiO2表面上的-NH2形成化學作用力，-NH2在溶液中以質子化的-NH3+形式存在，而-NH3+中的H+與NH4+進行離子交換達吸附效果，而再生方面，相較於酸基為基礎吸附材再生容易造成二次污染，本研究以簡單的100℃加熱方式使NH4+脫附達到再生效果，再生率為74.5%。

In this study, amino-functionalized silica (NH2-SiO2) was prepared as the adsorbent for NH4+ removal for the first time. Tetraethyl orthosilicate (TEOS) and 3-Aminopropyltriethoxysilane (APTES) were used as the precursor for SiO2 and the source of -NH2 functional groups, respectively. From the FTIR spectra, the wavenumber of 798 cm-1 in the pure SiO2 sample represented the Si-O-Si bonding, while in the NH2-SiO2 powders with different APTES：TEOS ratios, additional N-H bonds at 694cm-1 indicates that -NH2 was successfully modified on the SiO2 particles. When the APTES：TEOS ratio increased from 0：5 to 20：5, the NH4 + adsorption amount increased from an undetectable value to 9.85 mg/g, implying that -NH2 is an active adsorption site for NH4+ ions. The adsorption behavior and mechanism of NH2-SiO2 were investigated through kinetic adsorptions, isothermal adsorptions, and FTIR characterization. The kinetics was better fitted by the pseudo-second-order model with R2= 0.997. Adsorption isotherm was better fitted by the Langmuir model with R2= 0.984 and the maximum adsorption capacity of 11.53 mg/g. These results reveal that the rate-limiting step is the chemical reaction between NH4+ and -NH2. Most of -NH2 are in the form of -NH3+ in the solution, and the H+ ions on the -NH3+ groups were exchangeable with NH¬4+ ions. In the aspect of regeneration, the NH4+ desorption can be achieved by simple heating at 100℃ and the regeneration efficiency was 74.5%.

摘要 I
Abstract II
致謝 III
圖目錄 VI
表目錄 VII
第一章 前言 1
1.1 研究動機 1
1.2 研究目的 2
第二章 文獻回顧 4
2.1 NH4+來源、危害及處理方法 4
2.2 NH4+/NH3吸附材 5
2.3 吸附機制 9
2.4 吸附熱力學 10
2.5 吸附動力學 13
2.6 環境影響因子 15
2.6.1 溶液pH值 15
2.6.2 初始濃度 15
2.6.3 反應時間 16
2.6.4 吸附劑劑量 16
2.6.5 反應溫度 16
2.7 NH2-SiO2 17
第三章 研究材料與方法 19
3.1 實驗架構 19
3.2 實驗材料 20
3.3 NH2-SiO2合成方法 20
3.4 NH2-SiO2表面特性分析 21
3.4.1氮氣吸脫附分析 21
3.4.2傅立葉轉換紅外光譜分析(FTIR) 22
3.4.3表面電位及等電位點之分析(pHzpc) 22
3.4.4化學分析電子光譜分析(XPS) 22
3.4.5高解析場發射掃描式電子顯微鏡及能量散佈光譜儀(SEM-EDS) 23
3.5 NH2-SiO2吸附實驗 23
3.5.1 NH4+溶液之配製 23
3.5.2吸附動力實驗 23
3.5.3等溫吸附實驗 24
3.5.4 pH實驗 24
3.5.5 離子層析儀之分析條件 24
3.6 NH2-SiO2脫附及再生實驗 24
第四章 結果與討論 25
4.1材料特性鑑定 25
4.2 NH4+吸附實驗 29
4.2.1 動力吸附實驗 31
4.2.2 等溫吸附實驗 33
4.2.3 NH4+溶液pH值影響實驗 36
4.2.4 NH4+吸附機制 38
4.3 NH4+脫附及再生實驗 40
第五章 結論 42
參考文獻 43
附錄A NH2-SiO2元素濃度比例 47

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